Massive Preparation of Coumarone-indene Resin-based Hyper-crosslinked Polymers for Gas Adsorption

Hyper-crosslinked polymers(HCPs) are promising materials for gas capture and storage because of their low cost and easy preparation. In this work, we report the massive preparation of coumarone-indene resin-based hyper-crosslinked polymers via one-step Friedel-Crafts alkylation. Low-cost coumarone-indene resin serves as the new building block and chloroform is employed as both solvent and external crosslinker. A maximum surface area of 966 m~2·g~(-1) is achieved, which is comparable with that of previously-reported coal tar-based porous organic polymers. Most importantly, a large number of heteroatoms including inherent oxygen atoms and introduced chlorine atoms in obtianed HCPs further enhance the interaction between specific sorbate molecule and adsorbent. Therefore, optimal structural and chemical property endow the new coumarone-indene resin-based HCPs with decent gas storage capacity(14.60 wt% at273 K and 0.1 MPa for CO_2; 1.18 wt% at 77.3 K and 0.1 MPa for H_2). These results demonstrate that new HCPs are potential candidates for applications in CO_2 and H_2 capture.     

Synthesis and evaluation of N,O‐doped hypercrosslinked polymers and their performance in CO2 capture

A series of N, O‐doped hypercrosslinked microporous polymers (HCPs) with high surface area and rich microporosity were constructed via facile Friedel‐Crafts alkylation promoted by anhydrous ferric chloride (FeCl₃), which used benzyl alcohol (BA) and 2‐phenylimidazole (PID) as the basic building blocks. The effects of structural composition on the pore properties and gas adsorption properties of prepared HCPs were systematically investigated. The results show that by adjusting the ratio of PID to BA, the Brunauer–Emmett–Teller (BET) specific surface area and pore volume of the prepared HCPs can be controlled, and the BET specific surface area of the polymers range from 732–992 m²/g. Gas uptake experiments indicate that the obtained HCPs exhibit very high CO₂ adsorption capacity up to 3.55 mmol/g at 273 K/1.0 bar. Simultaneously, these N, O‐doped HCPs also show quite high isosteric heat of CO₂ sorption at the low coverage (up to 33 kJ/mol). In addition, the prepared HCPs have excellent selective adsorption performance, and the optimal selective adsorption of CO₂/N₂ is 62. These results demonstrate that these prepared HCPs are potential candidates for applications in CO₂ capture.     

The preparation of hyperbranched aromatic and aliphatic polyether epoxies by chloride‐catalyzed proton transfer polymerization from ABn and A2 + B3 monomers

Hyperbranched polymers consisting of aromatic or aliphatic polyether cores and epoxide chain‐end peripheries were prepared by proton transfer polymerization. AB₂ diepoxyphenol monomer 1 proved to be well suited for the preparation of hyperbranched aromatic polymer 2 by this proton transfer polymerization. The use of chloride‐ion catalysis, rather than conventional base catalysis, for the preparation of polymers from diepoxyphenol 1 offered a unique method to control the ultimate molecular weight of the polymer product through variations of the initial concentration of monomer 1 in tetrahydrofuran. An alternative route to hyperbranched polyether epoxies made use of commercially available or easily prepared aliphatic monomers of the types AB₂, AB₃, and A₂ + B₃. Although these aliphatic polymerizations can be initiated with a base, chloride‐ion catalysis proved most effective for controlling the polymerization. The hyperbranched epoxies were characterized by NMR spectroscopy, gel permeation chromatography, and multi‐angle laser light scattering. Chemical modification of the polymers after polymerization was carried out via nucleophilic addition on the epoxide groups or derivatization of the hydroxy substituents within the hyperbranched polymer structure. Spectroscopic measurements suggested that some such ring‐opened materials may adopt reverse unimolecular micellar structures in appropriate solution environments. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4850–4869, 2000     

Topotactic Synthesis of Phosphabenzene‐Functionalized Porous Organic Polymers: Efficient Ligands in CO2 Conversion

Progress toward the preparation of porous organic polymers (POPs) with task‐specific functionalities has been exceedingly slow—especially where polymers containing low‐oxidation phosphorus in the structure are concerned. A two‐step topotactic pathway for the preparation of phosphabenzene‐based POPs (Phos‐POPs) under metal‐free conditions is reported, without the use of unstable phosphorus‐based monomers. The synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease. As an example, partially fluorinated Phos‐POPs (F‐Phos‐POPs) were obtained with a surface area of up to 591 m² g^?1. After coordination with Ru species, a Ru/F‐Phos‐POPs catalyst exhibited high catalytic efficiency in the formylation of amines (turnover frequency up to 204 h^?1) using a CO₂/H₂ mixture, in comparison with the non‐fluorinated analogue (43 h^?1) and a Au/TiO₂ heterogeneous catalysts reported previously (<44 h^?1). This work describes a practical method for synthesis of porous organic phosphorus‐based polymers with applications in transition‐metal‐based heterogeneous catalysis.     

Controlled Anisotropic Growth of Co‐Fe‐P from Co‐Fe‐O Nanoparticles

A facile approach to bimetallic phosphides, Co‐Fe‐P, by a high‐temperature (300 °C) reaction between Co‐Fe‐O nanoparticles and trioctylphosphine is presented. The growth of Co‐Fe‐P from the Co‐Fe‐O is anisotropic. As a result, Co‐Fe‐P nanorods (from the polyhedral Co‐Fe‐O nanoparticles) and sea‐urchin‐like Co‐Fe‐P (from the cubic Co‐Fe‐O nanoparticles) are synthesized with both the nanorod and the sea‐urchin‐arm dimensions controlled by Co/Fe ratios. The Co‐Fe‐P structure, especially the sea‐urchin‐like (Co_0.54Fe_0.46)₂P, shows enhanced catalysis for the oxygen evolution reaction in KOH with its catalytic efficiency surpassing the commercial Ir catalyst. Our synthesis is simple and may be readily extended to the preparation of other multimetallic phosphides for important catalysis and energy storage applications.     

Metal Microporous Aromatic Polymers with Improved Performance for Small Gas Storage

A novel metal‐doping strategy was developed for the construction of iron‐decorated microporous aromatic polymers with high small‐gas‐uptake capacities. Cost‐effective ferrocene‐functionalized microporous aromatic polymers (FMAPs) were constructed by a one‐step Friedel–Crafts reaction of ferrocene and s‐triazine monomers. The introduction of ferrocene endows the microporous polymers with a regular and homogenous dispersion of iron, which avoids the slow reunion that is usually encountered in previously reported metal‐doping procedures, permitting a strong interaction between the porous solid and guest gases. Compared to ferrocene‐free analogues, FMAP‐1, which has a moderate BET surface area, shows good gas‐adsorption capabilities for H₂ (1.75 wt % at 77 K/1.0 bar), CH₄ (5.5 wt % at 298 K/25.0 bar), and CO₂ (16.9 wt % at 273 K/1.0 bar), as well as a remarkably high ideal adsorbed solution theory CO₂/N₂ selectivity (107 v/v at 273 K/(0–1.0) bar), and high isosteric heats of adsorption of H₂ (16.9 kJ mol^?1) and CO₂ (41.6 kJ mol^?1).     

Two‐Dimensional Core‐Shelled Porous Hybrids as Highly Efficient Catalysts for the Oxygen Reduction Reaction

Two‐dimensional (2D) transition‐metal dichalcogenides (TMDs) have drawn much attention due to their unique physical and chemical properties. Using TMDs as templates for the generation of 2D sandwich‐like materials with remarkable properties still remains a great challenge due to their poor solvent processability. Herein, MoS₂‐coupled sandwich‐like conjugated microporous polymers (M‐CMPs) with high specific surface area were successfully developed by using functionalized MoS₂ nanosheets as template. As‐prepared M‐CMPs were further used as precursors for preparation of MoS₂‐embedded nitrogen‐doped porous carbon nanosheets, which were revealed as novel electrocatalysts for oxygen reduction reaction with mainly four‐electron transfer mechanism and ultralow half‐wave potential in comparison with commercial Pt/C catalyst. Our strategy to core–shelled sandwich‐like hybrids paves a way for a new class of 2D hybrids for energy conversion and storage.     

Modular In Situ Functionalization Strategy: Multicomponent Polymerization by Palladium/Norbornene Cooperative Catalysis

Herein, we report a cooperatively palladium/norbornene‐catalyzed polymerization, which simplifies the synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A₂B₂C‐type multicomponent polymerization that is based on an ortho amination/ipso alkynylation reaction was developed for the preparation of various amine‐functionalized arylacetylene‐containing polymers. Within a single catalytic cycle, the amine side chains are site‐selectively installed in situ by C?H activation during the polymerization process, which represents a major difference from conventional cross‐coupling polymerizations. This “in situ functionalization” strategy enables the modular incorporation of functional side chains starting from simple monomers, thereby conveniently affording a diverse range of functional polymers.     

多孔聚合物贮氢材料的研究进展

微孔聚合物由于具有较高的比表面积,因此可用作物理吸附贮氢材料.本文通过比较0.1MPa、77K下自具微孔聚合物、超交联聚合物等多孔聚合物与其它多孔贮氢材料(如碳材料、金属有机网络等)的贮氢性能,阐述了比表面积、孔尺寸及孔形貌、与氢气的作用力等因素对多孔聚合物贮氢量的影响,由于合成超交联聚合物的单体多且孔形貌容易控制,因此超交联聚合物成为具有发展潜力的贮氢聚合物.     

Hypercrosslinking Polymers Fabricated from Divinyl Benzene via Friedel-Crafts Addition Polymerization

Microporous organic polymers with high surface area are widely used in many applications.Among them,hypercrosslinked polymers have been extensively concerned because of their simple processes and low-cost reagents.However,due to most state-of-the-art strategies for HCPs based on condensation reactions,the release of small molecules such as hydrochloric acid and methanol involved in such strategies brings about new hazards to environment.Herein,we propose a method of fabrication of hypercrosslinked polymers via self-addition polymerization of divinyl benzene and its crosslinking with polar aromatic molecules.The hypercrosslinked polyDVB-based products are demonstrated by FriedelCrafts addition reaction of double bonds on DVB that can connect adjacent phenyl rings of aromatic molecules to form the crosslinked networks.The HCPDVB-CB obtained in 1-chlorobutane as solvent has a high micropore content and displays high surface area up to 931 m²/g.Following this finding,DVB is used as a novel external crosslinker for knitting polar aromatic molecules.When L-phenylalanine and bisphenol A are used as the aromatic units,the obtained HCP(Phe-DVB)and HCP(BPA-DVB)could reach surface area of 612 and 471 m²/g,and have hydrogen uptake of0.62 wt%and 0.58 wt%at 77 K and 1.13 bar by comparison with HCPDVB-CB having hydrogen uptake of 0.30 wt%,respectively.     

Novel Functional Conjugative Hyperbranched Polymers with Aggregation‐Induced Emission: Synthesis Through One‐Pot “A2+B4” Polymerization and Application as Explosive Chemsensors and PLEDs

With the aim to develop new tetraphenylethylene (TPE)‐based conjugated hyperbranched polymer, TPE units, one famous aggregation‐induced emission (AIE) active group, are utilized to construct hyperbranched polymers with three other aromatic blocks, through an “A₂+B₄” approach by using one‐pot Suzuki polycondensation reaction. These three hyperbranched polymers exhibit interesting AIEE behavior and act as explosive chemsensors with high sensitivity both in the nanoparticles and solid states. This is the first report of the AIE activity of the TPE‐based conjugated hyperbranched polymers. Their corresponding PLED devices also demonstrate good performance.     

Amino‐functionalized hollow microporous organic nanospheres for pd supported catalysis and I2 uptake

Amino‐functionalized hollow microporous organic nanospheres (NH₂‐HMONs) were successfully synthesized by a combination of hyper‐crosslinking mediated self‐assembly process and a post‐modification strategy. Benefiting from amino groups and hollow microporous structure, the resultant NH₂‐HMONs can be used to immobilize Pd nanoparticles (Pd@NH₂‐HMONs) and enhance the adsorption capacity for iodine. The obtained Pd@NH₂‐HMONs exhibited outstanding catalytic activity for hydrogenation of nitroarenes to aniline analogues. This strategy represents a new method for the preparation of porous organic polymers with special morphologies and functionalizations for potential applications including adsorption, separation, and catalysis. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2045–2052     

New organosoluble and thermally stable poly(amide‐imide)s with benzoxazole or benzothiazole pendent groups: synthesis and characterization

Two new benzoxazole or benzothiazole‐containing diimide‐dicarboxylic acid monomers, such as 2‐[3,5‐bis(N‐trimellitimidoyl)phenyl]benzoxazole ( 2 _o ) or 2‐[3,5‐bis(N‐trimellitimidoyl)phenyl]benzothiazole ( 2 _s ) were synthesized from the condensation reaction between 3,5‐diaminobenzoic acid and 2‐aminophenol or 2‐aminothiophenol in polyphosphoric acid (PPA) with subsequent reaction of trimellitic anhydride in the presence of glacial acetic acid, respectively, and two new series of modified aromatic poly(amide‐imide)s were prepared. This preparation was done with pendent benzoxazole or benzothiazole units from the newly synthesized diimide‐dicarboxylic acid and various aromatic diamines by triphenyl phosphite‐activated polycondensation. In addition, the corresponding unsubstituted poly(amide‐imide)s were prepared under identical experimental conditions for comparative purposes. Characterization of polymers was accomplished by inherent viscosity measurements, FT‐IR, UV–visible, ¹H‐NMR spectroscopy and thermogravimetry. The polymers were obtained in quantitative yields with inherent viscosities between 0.39 and 0.81 dl g^?1. The solubilities of modified poly(amide‐imide)s in common organic solvents as well as their thermal stability were enhanced compared to those of the corresponding unmodified poly(amide‐imide)s. The glass transition temperature, 10% weight loss temperature, and char yields at 800°C were, respectively, 7–26°C, 17–46°C and 2–5% higher than those of the unmodified polymers. Copyright © 2010 John Wiley & Sons, Ltd.     

Gas‐Separation Membranes Loaded with Porous Aromatic Frameworks that Improve with Age

Porosity loss, also known as physical aging, in glassy polymers hampers their long term use in gas separations. Unprecedented interactions of porous aromatic frameworks (PAFs) with these polymers offer the potential to control and exploit physical aging for drastically enhanced separation efficiency. PAF‐1 is used in the archetypal polymer of intrinsic microporosity (PIM), PIM‐1, to achieve three significant outcomes. 1) hydrogen permeability is drastically enhanced by 375 % to 5500 Barrer. 2) Physical aging is controlled causing the selectivity for H₂ over N₂ to increase from 4.5 to 13 over 400 days of aging. 3) The improvement with age of the membrane is exploited to recover up to 98 % of H₂ from gas mixtures with N₂. This process is critical for the use of ammonia as a H₂ storage medium. The tethering of polymer side chains within PAF‐1 pores is responsible for maintaining H₂ transport pathways, whilst the larger N₂ pathways gradually collapse.     

Novel fluorinated polymers by radical polyaddition: Inspiration and progress

The story of the outset and the growth of radical polyaddition of bisperfluoroisopropenyl derivatives [CF₂?C(CF₃)? R? C(CF₃)? CF₂] with several organic compounds possessing carbon–hydrogen bonds is described. The reaction afforded novel fluorinated polymers bearing such organic segments in polymer main chains as 1,4‐dioxane, diethyl ether, dimethoxyethane, 18‐crown‐6, triethylamine, glutaraldehyde, and alkanes which have never been supposed as direct starting compounds for preparation of polymers. The facile method for preparation of fluorinated hybrid polymers bearing alkylsilyl groups was developed with diethoxydimethylsilane and silsesquioxanes. Taking advantage of the high reactivity of the perfluoroisopropenyl group as a radical acceptor, self‐polyaddition and cyclopolymerization were investigated. Triethysilyl perfluoroisopropenyl ether [CF₂? C(CF₃)? O? Si(C₂H₅)₃] was proved to be the most probable candidate for self‐polyaddition. Cyclopolymerization of perfluoroisopropenyl vinylacetate [CF₂?C(CF₃) OCO? CH₂CH? CH₂] was investigated to afford polymers possessing five‐membered‐ring units in main chains. The interconversion of the unstable fluorinated carbon radical and the stable hydrocarbon radical had an important role in the reaction. The radical addition reaction presented herein may be developed for preparation of a wide variety of novel fluorinated polymers and organic compounds possessing functional groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4101–4125, 2004     

Designing Branched Deoxybenzoin Polyesters as Polymeric Flame Retardants

AB₂ monomers present opportunities to conduct one‐pot syntheses of highly branched or “hyperbranched” polymers, which are known for their distinct physical and chemical properties relative to linear polymers. This paper describes the synthesis of a deoxybenzoin‐containing AB₂ monomer and its use in step‐growth polymerization to prepare branched aromatic polyesters. Highly soluble deoxybenzoin polymers were obtained with degrees of branching reaching 0.36 and estimated molecular weights approaching 20 kDa. The phenolic chain ends of the polymer allowed for post‐polymerization modification by silylation and esterification chemistry. TGA and microscale combustion calorimetry revealed these novel aromatic polyesters to possess the critically important characteristics of flame‐retardant polymers, such as high char yield and low heat release. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1765–1770     

Synthesis of aromatic poly(ether amide amide ether ketone ketone)s by electrophilic Friedel–Crafts solution polycondensation

A new monomer, N,N′‐bis(4‐phenoxybenzoyl)‐p‐phenylenediamine (BPBPPD), was prepared by the condensation of p‐phenylenediamine with 4‐phenoxybenzoyl chloride in N,N‐dimethylacetamide (DMAc). Novel aromatic poly(ether amide amide ether ketone ketone)s (PEAAEKKs) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of BPBPPD with a mixture of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC), over a wide range of TPC/IPC molar ratios, in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The influences of reaction conditions on the preparation of polymers were examined. The polymers obtained were characterized by different physico–chemical techniques such as FT‐IR, Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), and wide angle X‐ray diffraction (WAXD). The polymers with 70–100 mol% IPC are semicrystalline and have remarkably increased T_gs over commercially available poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK) due to the incorporation of amide groups in the main chain. The polymers with 70–80 mol% IPC had not only high T_gs of 209–213°C, but also moderate T_ms of 339–348°C, which are suitable for melt processing. The polymers with 70–80 mol% IPC had tensile strengths of 107.5–109.8 MPa, Young's moduli of 2.53–2.69 GPa, and elongations at break of 9–11% and exhibited high thermal stability and good resistance to organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.     

Metalloporphyrin‐Based Hypercrosslinked Polymers Catalyze Hetero‐Diels–Alder Reactions of Unactivated Aldehydes with Simple Dienes: A Fascinating Strategy for the Construction of Heterogeneous Catalysts

We describe a novel and intriguing strategy for the construction of efficient heterogeneous catalysts by hypercrosslinking catalyst molecules in a one‐pot Friedel–Crafts alkylation reaction. The new hypercrosslinked polymers (HCPs) as porous solid catalysts exhibit the combined advantages of homogeneous and heterogeneous catalysis, owing to their high surface area, good stability, and tailoring of catalytic centers on the frameworks. Indeed, a new class of metalloporphyrin‐based HCPs were successfully synthesized using modified iron(III) porphyrin complexes as building blocks, and the resulting networks were found to be excellent recyclable heterogeneous catalysts for the hetero‐Diels–Alder reaction of unactivated aldehydes with 1,3‐dienes. Moreover, this new strategy showed wide adaptability, and many kinds of homogeneous‐like solid‐based catalysts with high catalytic performance and excellent recyclability were also constructed.     

Oligomeric aliphatic–aromatic ether containing phthalonitrile resins

A versatile synthetic method has been developed for oligomeric aliphatic–aromatic ether containing phthalonitrile (PN) resins and applied to the preparation of three unique resin systems. The oligomeric PN monomers were prepared from the reaction of an excess amount of bisphenol A with a dihalo‐aliphatic containing compound in the presence of K₂CO₃ in dimethylsulfoxide, followed by end‐capping with 4‐nitrophthalonitrile in a two‐step, one‐pot reaction. These PN resin systems exhibited excellent viscosities for molding various shaped articles after thermal curing to yield crosslinked polymers. These polymers offered more mechanical flexibility, when compared with an all aromatic backbone, while still maintaining good thermal stability, dielectric properties, and low water absorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2186–2191     

Tetrablock Metallopolymer Electrochromes

Multi‐block polymers are highly desirable for their addressable functions that are both unique and complementary among the blocks. With metal‐containing polymers, the goal is even more challenging insofar as the metal properties may considerably extend the materials functions to sensing, catalysis, interaction with metal nanoparticles, and electro‐ or photochrome switching. Ring‐opening metathesis polymerization (ROMP) has become available for the formation of living polymers using highly efficient initiators such as the 3rd generation Grubbs catalyst [RuCl₂(NHC)(=CHPh)(3‐Br‐C₅H₄N)₂], 1 . Among the 24 possibilities to introduce 4 blocks of metallopolymers into a tetrablock metallocopolymer by ROMP using the catalyst 1 , two viable pathways are disclosed. The synthesis, characterization, electrochemistry, electron‐transfer chemistry, and remarkable electrochromic properties of these new nanomaterials are presented.